This invention relates to a process for the separation of a gas containing hydrocarbons.
Ethylene, ethane, propylene, propane and/or heavier hydrocarbons can be recovered from a variety of gases, such as natural gas, refinery gas, and synthetic gas streams obtained from other hydrocarbon materials such as coal, crude oil, naphtha, oil shale, tar sands, and lignite. Natural gas usually has a major proportion of methane and ethane, i.e., methane and ethane together comprise at least 50 mole percent of the gas. The gas also contains relatively lesser amounts of heavier hydrocarbons such as propane, butanes, pentanes and the like, as well as hydrogen, nitrogen, carbon dioxide and other gases.
The present invention is generally concerned with the recovery of ethylene, ethane, propylene, propane and heavier hydrocarbons from such gas streams. A typical analysis of a gas stream to be processed in accordance with this invention would be, in approximate mole percent, 88.41% methane, 6.65% ethane and other C2 components, 2.26% propane and other C3 components, 0.36% iso-butane, 0.45% normal butane, 0.31% pentanes plus, with the balance made up of nitrogen and carbon dioxide. Sulfur containing gases are also sometimes present.
The historically cyclic fluctuations in the prices of both natural gas and its natural gas liquid (NGL) constituents have at times reduced the incremental value of ethane, ethylene, propane, propylene, and heavier components as liquid products. Competition for processing rights has forced plant operators to maximize the processing capacity and recovery efficiency of their existing gas processing plants. Available processes for separating these materials include those based upon cooling and refrigeration of gas, oil absorption, and refrigerated oil absorption. Additionally, cryogenic processes have become popular because of the availability of economical equipment that produces power while simultaneously expanding and extracting heat from the gas being processed. Depending upon the pressure of the gas source, the richness (ethane, ethylene, and heavier hydrocarbons content) of the gas, and the desired end products, each of these processes or a combination thereof may be employed.
The cryogenic expansion process is now generally preferred for natural gas liquids recovery because it provides maximum simplicity with ease of start up, operating flexibility, good efficiency, safety, and good reliability. U.S. Pat. Nos. 3,292,380; 4,157,904; 4,171,964; 4,185,978; 4,251,249; 4,278,457; 4,519,824; 4,617,039; 4,687,499; 4,689,063; 4,690,702; 4,854,955; 4,869,740; 4,889,545; 5,275,005; 5,555,748; 5,568,737; 5,771,712; 5,799,507; 5,881,569; 5,890,378; 5,983,664; reissue U.S. Pat. No. 33,408; and co-pending application Ser. No. 09/439,508 describe relevant processes (although the description of the present invention in some cases is based on different processing conditions than those described in the cited U.S. patents and patent applications).
In a typical cryogenic expansion recovery process, a feed gas stream under pressure is cooled by heat exchange with other streams of the process and/or external sources of refrigeration such as a propane compression-refrigeration system. As the gas is cooled, liquids may be condensed and collected in one or more separators as high-pressure liquids containing some of the desired C2+ components. Depending on the richness of the gas and the amount of liquids formed, the high-pressure liquids may be expanded to a lower pressure and fractionated. The vaporization occurring during expansion of the liquids results in further cooling of the stream. Under some conditions, pre-cooling the high pressure liquids prior to the expansion may be desirable in order to further lower the temperature resulting from the expansion. The expanded stream, comprising a mixture of liquid and vapor, is fractionated in a distillation (demethanizer) column. In the column, the expansion cooled stream(s) is (are) distilled to separate residual methane, nitrogen, and other volatile gases as overhead vapor from the desired C2 components, C3 components, and heavier hydrocarbon components as bottom liquid product.
If the feed gas is not totally condensed (typically it is not), at least a portion of the vapor remaining from the partial condensation can be passed through a work expansion machine or engine, or an expansion valve, to a lower pressure at which additional liquids are condensed as a result of further cooling of the stream. The pressure after expansion is essentially the same as the pressure at which the distillation column is operated. The combined vapor-liquid phases resulting from the expansion are supplied as a feed to the column. In recent years, the preferred processes for hydrocarbon separation involve feeding this expanded vapor-liquid stream at a mid-column feed point, with an upper absorber section providing additional rectification of the vapor phase. There are, however, processes wherein this expanded vapor-liquid stream is used as the top column feed. Typically, the vapor portion of the expanded stream and the demethanizer overhead vapor combine in an upper separator section in the fractionation tower as residual methane product gas. Alternatively, the cooled and expanded stream may be supplied to a separator to provide vapor and liquid streams, so that thereafter the vapor is combined with the tower overhead and the liquid is supplied to the column as a top column feed.
For those processes that include an upper rectification section, a reflux stream must be provided for the section. One manner for accomplishing this is to withdraw a vapor distillation stream from the upper section of the demethanizer tower, cool it to partially condense it by heat exchange with other process streams, e.g., part of the feed gas that has been cooled to substantial condensation and then expanded to cool it further. The liquid condensed from the vapor distillation stream is then supplied as the top feed to the demethanizer.
The purpose of this process is to perform a separation that produces a residue gas leaving the process which contains substantially all of the methane in the feed gas with essentially none of the C2 components and heavier hydrocarbon components, and a bottoms fraction leaving the demethanizer which contains substantially all of the C2 components and heavier hydrocarbon components with essentially no methane or more volatile components while meeting plant specifications for maximum permissible carbon dioxide content. The present invention provides a means for providing a new plant or modifying an existing processing plant to achieve this separation at significantly lower capital cost by reducing the size of or eliminating the need for a product treating system for removal of carbon dioxide. Alternatively, the present invention, whether applied in a new facility or as a modification to an existing processing plant, can be used to recover more C2 components and heavier hydrocarbon components in the bottom liquid product for a given carbon dioxide concentration in the feed gas than other processing schemes.
In accordance with the present invention, it has been found that C2 recoveries in excess of 66 percent can be maintained while maintaining the carbon dioxide content of the bottom liquid product within specifications and providing essentially complete rejection of methane to the residue gas stream. The present invention, although applicable at lower pressures and warmer temperatures, is particularly advantageous when processing feed gases at pressures in the range of 600 to 1000 psia or higher under conditions requiring column overhead temperatures of −120° F. or colder.
The present invention uses a modified reboiler scheme which can be applied to any type of NGL recovery system. In a typical reboiler or side reboiler application in a distillation column, the entire column down-flowing liquid stream is withdrawn from the tower and passed through a heat exchanger, then returned to the column at essentially the same point in the column. In this modified reboiler system, a portion of the column down-flowing liquid is withdrawn from a point higher in the column, i.e., separated from the return point by at least one theoretical stage. Even though the flow rate of the liquid may be lower, it is usually much colder and can have advantages in improving recovery or reducing exchanger size.
It has been found that when the present invention is applied to prior art processes for NGL recovery, the recovery of C2 components and heavier components is improved by one to two percent. The improvement in recovery is much greater, however, when it is desirable to reduce the carbon dioxide content in the recovered NGL product. Recovery of ethane in a typical NGL recovery plant also results in recovery of at least some of the carbon dioxide contained in the feed gas because carbon dioxide falls in between methane and ethane in relative volatility. Therefore, as ethane recovery increases, so does the recovery of carbon dioxide in the NGL product. By applying the modified reboiler scheme of the present invention, the applicants have found that it is possible to significantly improve recovery of ethane in the NGL product compared to use of the conventional reboiler or side reboiler systems when the column is reboiled to meet the desired carbon dioxide content in the NGL product.
In the following explanation of the above figures, tables are provided summarizing flow rates calculated for representative process conditions. In the tables appearing herein, the values for flow rates (in pound moles per hour) have been rounded to the nearest whole number for convenience. The total stream rates shown in the tables include all non-hydrocarbon components and hence are generally larger than the sum of the stream flow rates for the hydrocarbon components. Temperatures indicated are approximate values rounded to the nearest degree. It should also be noted that the process design calculations performed for the purpose of comparing the processes depicted in the figures are based on the assumption of no heat leak from (or to) the surroundings to (or from) the process. The quality of commercially available insulating materials makes this a very reasonable assumption and one that is typically made by those skilled in the art.